Aryloxy polyalkylene ether sulphonates



Patented Apr. 26 1938 POLYALKNE EITHER PHONATES Herman A. Bruson, Philadelphia, Pa., assignor to Riihm, & Haas Company, Philadelphia, Pa.

No Drawing. Application June 20, 1936, Serial No. 86,344

18 Claims. ((31. 260-150) This invention relates to aryloxy polyalkylene ether sulphonates having the general formula ROA(OA)n-O- A'SO3M in which R is an aromatic hydrocarbon radical, A represents alkylene groups having at least two carbon atoms, n is zero or one, and M is a metal.

It relates more particularly to the water-soluble salts of the above type which I have, found,

have a marked capillary activity and are useful V as textile assistants and as dispersing, emulsifying, wetting, cleansing, introfying, and spreading agents. a

The salts of this type are prepared by heating 5 a metal sulphite with an aryloxy polyalkylene ether chloride having the general formula in which X is a halogen atom. The product resulting from the condensation of the metal sulphite and the aryloxy polyalkylene ether halide is the salt of the corresponding sulphonic acid having the general formula in the presence of a strongly alkaline condensing agent under such conditions that only one of the halogen atoms is substituted by the aryloxy group. A process for preparing these halides is described in my copending application Serial No. 79,718, filed May 14, 1936.

For the purposes of the present invention the aromatic radical R of the aryloxy polyalkylene ether halide is derived from a phenol, or a naphthol such as phenol, o-, m-, or p-cresol, any of the isomeric xylenols, thymol, carvacrol, but preferably alkylor polyalkyl-substituted phenols such as any of the straight or branched chain butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl or octadecyl phenols or cre- .so1s; or the phenyl, cyclohexyl, and benzyl phenols; naphthol,v and similarly substituted naphthols.

In the dihalogeno polyalkylene ethers used for condensing with the above phenols, the alkylene groups have preferably two, three or four carbon' atoms which may be arranged in a. straight 66 chain or branched chain when the group has three or four carbon atoms. Among these dihalogeno polyalkylene ethers are p, p'-dichlorodiethyl. ether, '7, *y'-dichlorodipropyl ether, 5, 13'- dichlorodiisopropyl ether, fi-chloroethoxyethyl- [EV-chloroethyl ether, ClCHzCH2OCH2- CH2O CH2-CH2C1, p, 18'-dichlorodiisobutyl ether and their higher homologs. The corresponding dibromo and diiodo compounds may also be used, and with them the reaction can generally be carried out at av lower temperature.

The condensation between the metal sulphite and the aryloxy polyalkylene ether halide may be carried out in aqueous or aqueous-alcoholic solution. If the halide used is the chloride, the reaction is carried out preferably at a'temperature above C. (-190 C. is a good working range) at superatmospheric pressure, whereas if it be a bromide or iodide, the reaction may be conducted under a reflux condenser at ordinary pressure. Among the more readily available metal sulphites which can be used are the neutral sulphites of sodium and potassium. Other metal sulphites such as those of calcium, magnesium, zinc and copper can be used, but the water-soluble alkali metal sulphites are the most efficient and therefore sodium sulphite or potassium sulphite is preferred. The use of bisulphites or of ammonium sulphite leads respectively to break down products of the aryloxy polyalkylene ethers employed or to impure reaction products.

In order to illustrate more fully this invention,

the following examples are given.

Example 1 on, em

O3 -i-CHril-QO-CHz-ClIz-O-CHa-Cflr-SOM In an enameled iron autoclave fitted with an agitator there was placed 100 g. of p-ter-octylphenoxyethoxyethyl chloride together with 406 cc. of water and 46 g. of sodium sulphite (NazSOa) The mixture was stirred and heated at 150-160 C. for sevenhours- The pressure developed was about 90 lbs. per square inch.

At the end of this time,'the product was completely soluble in water. It had the consistency sulphonate, in addition to having a high wettingout action, is useful as an emulsifying and spreading agent for oil-soluble contact insecticides, such as organic thiocyanates. It may also be used as a leveling agent in dyeing.

A mixture of 128 g. of p-ter-butylphenoxyethoxyethyl chloride, 66 g. of sodium sulphite and A mixture of 34 g. of p-(,,' ,'.y-tetramethylbutyl) phenoxy-isopropoxy-isopropyl chloride was heated at 170 C. for six hours in a steel autoclave with 13 g. of sodium sulphite and 150 cc. of water, under constant agitation.

The white, soap-like mass obtained is useful as a detergent and emulsifying agent.

The potassium salt is also a soapy solid and is readily obtained by using 17 g. of potassium sulphite in place of the sodium sulphite above.

Example 6 One mol. equivalent of either 0- or p-phenyl phenoxyethoxyethyl chloride when heated with one mol. equivalent of sodium sulphite or potassium sulphite and water at 150-160 C. under pressure as described in the previous examples yields a water-soluble sulphonate of the above formula useful as a wetting-out agent.

Example 7 CHI-CH1 400 cc. of water was heated in an iron autoclave while stirring rapidly for 4 hours at 155-160 C.

The pressure rose to about lbs. per square inch.

The product was dried and extracted with boiling alcohol. Upon cooling, the sodium p-terbutylphenoxyethoxyethyl sulphonate crystallized in colorless plates. It is very soluble in water. The aqueous solution is very foamy and soap-like, gives no precipitate with soluble calcium or magnesium salts or hard water, and can be used" as a spreading agent for contact insecticides.

The potassium salt is a water-soluble crystalline material and is prepared in the same manner.

Example 3 One mol. equivalent of either 0- or p-cyclo- -hexylphenoxyethoxyethyl chloride when heated with one mol. equivalent of sodium sulphite or potassium sulphite at 150-160 C. for six to eight hours with water inan autoclave as described in the previous examples yields a water-soluble, soapy sulphonate having capillary active properties.

Example 8 29 g. of o-benzylphenoxyethoxyethyl chloride and 12.7 g. of sodium sulphite in cc. of water A mixture of g. of p-ter-amylphenoxyethoxyethyl chloride, 66 g. of sodium sulphite and 375 cc. of water was heated eight .hours at -160 C. at 90-93 lbs. per square inch pressure while stirring constantly in an enameled steel autoclave.

A water-soluble, creamy mass was obtained, which foams readily in solution and is well adapted for use as a wetting-out agent or as an assistant in dyeing or bleaching operations. It can be concentrated to a waxy solid.

Example 4 was heated at -165 C. for four hours in an iron autoclave. The water soluble sodium sulphonate has capillary active properties.

In the same manner, the p-benzylphenoxyethoxyethyl chloride yields the corresponding sodium sulphonate.

Example 9 I O-GHPCHFO-CHg-CHz-S OaM One mol. equivalent of p-naphthoxyethoxyethyl CHFC (CHQF'CH C (CHahOO-CHz-CHr-0CH:CHr-OCHr-CHz-S OzNB A mixture of 126 g. of p-ter-octylphenoxyethoxyethylchloroethyl ether, 43.8 g. of NazSOa (96% pure) and 400 cc. of water was heated in an iron autoclave at 155 C. for six hours while stirring rapidly.

A water-soluble soap-like mass was obtained having good detergent and wetting-out properties.

Example 5 chloride, 1.05 mols of sodium sulphite and 400 cc. of water were heated together while stirring at 160 C. in an enameled iron autoclave for five hours. The solution of the water-soluble sodium sulphonate obtained was evaporated to dryness and extracted with alcohol to free it from sodium chloride. Upon removal of the alcohol, the pure compound was obtained. It can be used as a wetting-out agent. The corresponding potassium sulphonate is likewise a capillary active compound.

Example 10 One mol.,equivalent each of sodium sulphite and p-ter-butylphenoxyethoxyethyl bromide was boiled under reflux in a mixture of equal'volumes of water and alcohol in the presence'of 1% of copper powder for 22 hours. The product obtained was a water-soluble sulphonate identical with that described in Example 2.

Example 11 CH: CHs

CH: CH:

A mixture of 123.5 g. of a,,' -tetramethy1- butylcresyloxyethoxyethyl p'- chloroethyl I ether, 43.8 g. of NazSOa and 400 cc. of water was heated for eight hours in a steel autoclave while constantly agitating at 150-160 C. Pressure 90-100 lbs/sq. in. The white, soap-like mass obtained is a good detergent and emulsifying agent.

- The tetramethylbutylcresyloxyethoxyethyl-fi'- chloroethyl ether used above was obtained by condensing fi-chloroethoxyethyl p chloroethyl ether with u ,-y,'y-tetramethylbutyl-o-creso1 in the presence of caustic soda. v

Example A mixture of 226.7 g. of p-sec-octylphenoxyethoxyethyl chloride, 92 g. of NazSOa and 800 cc.

sponding straight chain alkyl phenols, cresols,

xylenols or naphthols can be used.

. Example 14 0.3,:O-o-om-om-o-om4in-s 03M 1 mol. of n-hexadecylphenoxyethoxyethyl chloride is heated with 1 mol. equivalent of potassium sulphite in 1 liter of water at 180-190 C. with stirring in an iron autoclave at 200 lbs. pressure per square inch. After six and one-half hours I claim: 1. The compound having the formula 'of water was heated while stirring in a steel auto- 2. The compoundhaving the formula clave at 180-190 C. for four and one-half hours.

on; OH

H: v3. The compound having the formula cm on; Pressure rose'to 200 lbs/sq. in. The product was a viscous Water-soluble jelly'having marked detergent properties.

The p-sec-octylphenoxyethoxyethyl chloride was obtained by condensing p-sec-octylphenol with-excess g,p'-dichlorodiethyl ether in the presence of caustic soda.

J Example 13 A mixture of 1 molecular equivalent of p-terdodecylphenoxyethoxyethyl chloride (obtained by condensing tri-isobutylene with phenol and sulphuric acid and subsequently heating the product with excessfl,fl'-dich1orodiethyl ether and caustic soda), 1 mol. of anhydrous sodium sulphite and an equal volume of water was heated at 175-180 'C. with stirring in an autoclave for five hours. The product was a water-soluble soap.

-In place of the above compoundsthe corre- 4. A compound'of the general formula in which Z is a tertiary alkyl group having from 4 to 12 carbon atoms inclusive and M is an alkali metal.

5. 'A compound having the formula go-onwcnr-o-onr-onrs 01M in which Z is an alkyl, cycloalkyl, aralkylior aryl group and M isan alkali metal.

6. A compound having the formula in which R is a hydrocarbon radical containing an aryl group nuclearlyattached to the oxygen atom and M is an alkali metal.

7. Compounds of the general formula in which R is an aryl group containing as a nuclear substituent an alkyl radical having from four to eighteen carbon atoms inclusive, A rep- I resents alkylene groups containing from two to four carbon atoms'inclusive, n is one of the in-' tegers one and two, and M is an alkali metal.

8. Compounds of the general formula in which R is an aromatic hydrocarbon radical, A represents alkylene groups having at least two carbon atoms, 11 is one of the integers one and two, and M is an alkali metal.

9. Compounds of the general formula in which R is a phenyl group containing as a nuclear substituent' an alkyl radical having from four. to eighteen carbon atoms inclusive, A rep-, resents alkylene groups containing from two to four carbon atoms inclusive, n is one 01 the in tegers one and two, M is a metal of the group-consisting of the alkali and alkaline earth metals and it its valence.

' 10. Compounds of the general formula in which R is an 'aryl group containing as a nuclear substituent an alkyl radical having from four to eighteen carbon atoms inclusive, A represents alkylene groups containing from two to four carbon atoms inclusive, n is one of the integers one and two, M is a metal of the group consisting of the alkali and alkaline earth metals and :1: its valence.

11. Compounds of the general formula in which R is an aryl group containing as a nuclear substituent a member'of the group consisting of alkyl, cycloalkyl, aralkyl and aryl radicals, A represents alkylene groups containing from two to four carbon atoms inclusive, n is one of the integers oneand two, M is a metal of the group consisting of the alkali and alkaline earth metals and at its valence.

l2. Compounds of the general formula in which R is an aromatic hydrocarbon radical, A represents alkylene groups having at least two carbon atoms, 11. is one of the integers one and two, .M is a metal 01 the group consisting oi the alkali and alkaline earth metals and :2: its valence.

13. The process for preparing aryloxy polyalkylene ether sulphonates which comprises heating a metal sulphite of the group consisting of alkali and alkaline earth metal sulphites with an aryloxy polyalkylene ether halide of the general formula in which R is an aromatic hydrocarbon radical nuclearly attached to the oxygen atom, A repbon atoms, and n is one of the integers one two.

sents alkylene groups containing at least two carbon atoms, n is one of the integers one and two, and X is a halogen'atom'. v

15. The process for preparing arylon polyaryloxy alkylene ether sulphonates which comprises'heating at temperatures above 125 C. an alkali metal sulphite and an aryloxy polyalkylene ether chloride- 01' the general formula R(0A)n0A-Cl in which R is an aromatic hydrocarbon radical nuclearly attached to the oxygen atom, A represents alkylene groups containing at least two and two. i

16. The process for preparing aryloxy polyalkylene ether sulphonates which comprises heating at temperatures above 125 C. and at super- 7 carbon atoms, and n is one of the integers o'ne atmospheric pressure an alkali metal sulphite r and an aryloxy polyaikylene ether chloride or the general formula in which R is an varomatic hydrocarbon radical nuclearly attached to the oxygen atom, A represents alkylene groups containing at least two carbon atoms-and n is one of the integers one and two.

1'7. The process for preparing aryloxy polyalkylene ether sulphonates which comprises heating at temperatures above 125 C. and at superatmospheric pressure an aqueous solution of an alkali metal sulphite and an aryloxy polyalkylene ether halide of the general formula in which R is an aromatic hydrocarbon radical nuclearly attached to the oxygen atom, A represents alkylene groups containing at least two carand 18. The process of preparing alkylatedaryloxy polyalkylene ether sulphonates which comprises heating a mixture of an alkali metal sulphite with an equivalent amount of an alkylated aryloxy polyalkylene ether chloride in an aqueous medium at superatmospheric pressure.

HERMAN A. BRUSON. 

